Computer Applications in the Polymer Laboratory

Downloaded by 195.154.90.122 on March 28, 2016 | http://pubs.acs.org Publication Date: June 27, 1986 | doi: 10.1021/bk-1986-0313.ix002

Author Index Kah, A. F., 17 King, M. T., 105,114 Koehler, Mark E., 2,17,123 Krampe, Stephen E., 58 Lai, C. C, 275 MacGregor, J. F., 219 McCrackin, Frank L., 130 Mehta, J., 202 Mgaya, Alexander P., 288 Nathhorst, R. P., 155 Nave, M. D., 39 Niemann, T. F., 17 Penlidis, A., 219 Potenzone, Rudolph, Jr., 31 Provder, Theodore, 241 Rhodes, M. B., 155 Russell, Channing H., 23 Sebenik, Anton, 288 Timm, Delmar C., 187,275 Williams, T. R., 39 Wu, D. T., 170

Albrecht-Mallinger, Robert, 179 Barnes, John D., 130,140 Bauer, David R., 256 Boyd, Richard H., 89 Carlson, Gary M., 241 Clark, E. S., 140 Cloeter, M. D., 275 Constien, V. G., 105,114 Dickens, Brian, 130 Dickie, Ray A., 256 Doherty, David C., 31 Eaton, B. W., 275 Fellin, E. L., 105,114 Garcia-Rubio, L. H., 202 Gilbert, Richard E., 187 G i l l , T. T., 123 Golden, Joseph H., 6 Graves, G. G., 105 Hamielec, A. E., 219 Harwood, H. James, 288 Havriliak, Stephen, Jr., 76 Hild, David J., 187

Subject Index A

Analysis of mixture models, established techniques, 61 Analysis of styrene suspension polymerization continuous models, 210-211 efficiency, 211,212f,213 free volume theory, 215,217 initiator conversion vs. time, 215,2T6f initiator loadings, 211,2l4f kinetic parameters, 213,214t polydispersity, 210 total radical concentration, 211 variation of rate parameters as functions of conversion, 211,212f,213,2l6f variation of rate parameters vs. molecular weight, 215 Anhydride-cured epoxy polymerization, kinetic study, 275-287 Applications of mathematical dynamic model for emulsion polymerization processes batch and semibatch latex reactors, 225 continuous reactors and reactor trains, 225

Acrylic polymerization model capability, 172,173f description, 172 Administrative applications of data base management systems patent activity data base, 19 patent disclosure tracking data base, 19t Advantages of interfacing a viscoelastic device with a computer, 76-88 Advantages of modeling for coatings examinations of more options and more optimum options, 176 insights into problems impractical to probe experimentally, 176 means to correlate and communciate technical information, 176 minimization of experimental work, 176 routine application of complex theories, 175 training tool, 176 315

Provder; Computer Applications in the Polymer Laboratory ACS Symposium Series; American Chemical Society: Washington, DC, 1986.


316

COMPUTER APPLICATIONS IN THE POLYMER LABORATORY

Applications of mathematical dynamic model for emulsion polymerization processes—Continued on-line state estimation, optimal sensor selection, and control, 225-226 Applications programs for automated hydraulic fracturing fluid evaluation automatic operation of viscometer, 119 available programs, 118-119 data analysis report, 121 data-entry screen, 119,120f experiment setup f i l e , 119 manual operation of viscometer, 119,121 menu screen, 119,120f real-time data display screen, 121-122f shut down program, 121 Architecture of the batch control system, programs, 180-181f Automated method for hydraulic fracturing fluid evaluation application programs, 118-122 computer and instrument interface, 118 computer system, 1l6,117f,1l8 example data, 121,122f instrument design, 1l6,117f Automated rheology laboratory for fluid analysis computer control and data acquisition, 108-109 computer interface with instruments, 106 data analysis methods, 109-110 data storage and retrieval, 110 experimental setup, 108 Automotive enamels effect of cure on adhesion, 256-257 physical properties, 256

B Batch process control automated systems, 179-185 Behavior of silicone aerylate ^oligomers by designed experiments 2 fractional factorial design, 40,42t 2* full factorial central composite design, 51,55t correlation table, 42,46t final properties of optimized formulation, 56t histograms of responses from 2 fractional factorial design, 42,43f i n i t i a l property targets, 40,42t 3

u

Behavior of silicone acrylate oligomers by designed experiments—Continued limitations,.46,50 models for 2 fractional factorial design, 46,47t models for constrained mixture design, 50t,52f models from 23 f u l l factorial central composite design, 55,56t range-finding experiment, 40 regression analysis, 42,45f,51,52t response surface contour plot, 46-54 three-component constrained mixture design, 50t,52f Yates analysis, 42,44f Boundary region determination on tricoordinate contour plots constraints, 59 example of feasible region determination and rescaling, 60,6l,65f existence test of feasible region, 60 Scheffe model, 59

C Calibration for size-exclusion liquid chromatography, log hydrodynamic volume retention volume, 137,138f Chain statistics of a random monomer estimation, 34-35 example, 35-36f Chain-growth polymerizations, viscosity, 284 Chemical modeling laboratory, 32-36 CLINF0, description, 24 Coatings, modeling, 170-177 Cole-Cole phenomenological equation, application to isochronal mechanical relaxation scans, 91-92,93f Commerical testing laboratories economics of laboratory information management systems, 10 use in laboratory management information systems, 9 value of laboratory information management systems, 11 Complex algorithm-desirability function optimization advantages and disadvantages, 69 description, 69 three-component multiresponse optimization, 69-70,71-72f Complex method advantage, 62-63 analysis of four-component pesticide mixture, 63


317


INDEX Complex method—Continued correction factor, 63 features, 62 general procedure, 62 optimization of 11-component glass formulation, 64,66,67f optimization of four-component flare mixture, 63 Composition of hydraulic fracturing fluids, 105-106 Computer-aided design, benefits, 31 Computer simulation, definition, 171 Computer-assisted polymer design current uses, 37 goals, 38 modeling at the bench, 36-37 molecular modeling tools, 32-34 polymer model building, 34 Computer-interfaced optical microscopy basic characterization of the foam, 158-159 experimental materials, 158 fluorescence application, 157 fluorescence of polyurethane foams, 159 image analysis, 156-157 instrumentation, 156 interferometric methods, 157-158 mi crospectrophotometry, 157 stereology, 160-166 Consecutive reactions, kinetics, 241-254 Consistency index, calculation, 109-110 Constrained, multivariate optimization algorithms, drawbacks, 61-62 Continuous system modeling program development of self-condensation model, 295-310 output from print statement, 308,309f output of program A, 295,296f parameter evaluation, 297,298f program B description, 297,299 Control algorithm for a polystyrene reactor, 198,201 Cost analysis of laboratory information management systems cost-influencing factors, 12 costs vs. benefits, 13 total life-cycle cost, 12 Cost optimization for a polystyrene reactor, optimum combination of the inputs, 190-191 Crystallite orientation, X-ray diffraction, 140-153 Cure, oven optimization, 268-273 Cure chemistry applications, 242 effect of materials, 242 rate constants for each reaction, 242-243

Cure chemistry of epoxy polymerization, mechanism, 276-277 Cure in assembly ovens, 265-268 Cure window, measurement, 257 Cure windows, high-solids coatings vs. low-solids coatings, 265 D Data analysis for tensile testing, STRESS program, 124-125 Data base management systems acessibility, 18 administrative applications, 18,19t definition, 18 ease of use, 18 information retrieval applications, 19,20t laboratory applications, 20,21t personal applications, 22 scope of applications, 18 selection, 18 Data collection tasks for X-ray pole figure studies area scan, I46,l49f description, I46,l47t standard pole figure, 146,l48f 9 and 29 scan, 150,152f X and scan, 146 Data display functions for X-ray pole figure studies contour plotting routines, 148-I49f,150 description, 150 x-y plot, 150-151,152f Data handling for X-ray pole figure studies data bases, 143 functions, I43,l44f interface data base, 145 output data f i l e , 145-146 parameters, 143,145 pending task, 146 run data base, 145 spending task, 146 updating function for the specimen data base, 143 Data handling menu for size-exclusion liquid chromatography, 134-138 Data processing for X-ray pole figure studies, hardware and software, 151 Data reduction functions for size-exclusion liquid chromatography base-line drift, 135,137 control path, 135,136f problem, 135,138f Decoupling for a polystyrene reactor insertion of dynamic lag for Q, 191,192f



318


Decoupling for a polystyrene reactor—Continued system responses, 191,193,194f Design of mixed experiments boundary region determination on tricoordinate contour plots, 59-61 multiresponse mixture optimization, 66-72 objectives of a formulation, 61 single-response mixture optimization, 61-67 Designed experiments, behavior of silicone aerylate oligomers, 40-56 2-Dimethylol-o-cresol jH-NMR measurements, 292 H-NMR spectra of reaction mixtures, 292,294f H-NMR spectrum, 290,291f kinetic studies, 290,292,293f preparation, 290 self-condensation, 288 Disadvantages of modeling for coatings approximate nature of the results, 177 availability of physical properties data and model parameters, 177 long elasped time for development, 176 requires multidisciplinary approach, 176

E

Emulsion polymerization reactors, mathematical modeling, 219-238 Euler-Romberg integration method, concentration determination, 244 Experimential design for kinetic study of epoxy polymerization equipment, 280 resin, 280 Extensions of mathematical dynamic model for emulsion polymerization processes copolymer systems, 229,231f experimental recipes, 226t experimental results, 226,228f,230f other monomer systems, 226-230

F Fracture analysis for tensile testing, 125

G Global planning system for task automation, requirements, 4-5

H

Effect of first-order lag in Q, responses of system to changes in

Hardware for X-ray pole figure studies computer, 142 S and MW, 192f,193,194-195f diffracted intensity, 141-142 Effect of pole placement for a four-circle goniometer, 141 polystyrene reactor graphics printer, 142 performance function, 196 hardware configuration, I4l,l44f poles and time constants, 193,196t pulse-height analyze, 142 responses of system to changes in S specimen, 142 and MW, 198,199f X-ray and neutron state variable diffractometers, 141 feedback, 193,196,197f High-solids coatings, definition, 261 Effective cross-links, definition, 261 Hilds's performance function, Elastically effective cross-link definition, 196,198 density Homopolymerization reaction vs. bake temperature, 263,264f,265 engineering calculation, 261-262 kinetic models, 202 calculation for arbitrary bake objective, 202 histories for arbitrary Hyaluronic acid coatings, 261 monomers, 35 model verification for low-solids trimer, 36f coating, 263t,265 Hydraulic fracturing, 105-106 paint parameters, 263f Hydraulic fracturing fluid evaluation vs. physical measures of cure, 261 automated method, 115-122 Emulsion copolymerization model, 229 evolution of conventional Emulsion polymerization models, 220-224 method, 114-115


319

INDEX

Hydraulic fracturing fluid evaluation—Continued problems with conventional method, 115


I Information retrieval applications of data base management systems commercial data base, 20t laboratory notebook tracking data base, 20 research report index data base, 19,20t Initiator efficiencies, 203-204 Instrument automation development, 3 influence of microprocessors, 3 laboratory information management systems, 4 robotics systems, 3-4 Interface data base, description, 145 Internal rate of return, definition, 14 Isochronal mechanical relaxation scans advantages, 89-90 effect of activation energy on width of relaxation process, 90-91,93f effect of L on width of relaxation process, 91,93f interpretation of relaxation processes, 100,101f,102,103f parameter determination, 92 phenomenologi cal description, 91-92,93f rationale, 90-91 Isocyanate concentration vs. time, 242-243 isothermal cure curves, 246,247f Isothermal reactor, description, 188

K Kinetic model for cure optimization coatings, 257 extent of reaction vs. bake time, 258 mechanism of cross-linking of melamines, 258 reaction of coatings, 258 Kinetic model for polystyrene reactors, 187-188,I89t Kinetic reaction modeling for epoxy polymerization, 277-280 Kinetics of polymerization cure chromatograms, 28l,282f complexity of simulation, 285 correlation of monomer and polymer concentrations, 28l,283f

Kinetics of polymerization cure—Continued curing reactions, 276-277 effects of cure dynamics on molecular mobility, 276 experimental design, 280-281 functionality, 284 kinetic reaction modeling, 277-280 model improvement, 285-287 monomer dynamics, 28l,282f numerical simulation of cure dynamics, 285,286f population density distribution dynamics, 28l,283f reagents, 276

L Laboratory applications of data base management systems tracking of analytical sample analysis requests, 21 tracking of coatings test exposure data, 20,21t Laboratory automation, new perspective, 2-5 Laboratory information management system application of financial analytical methods, 6 in commercial testing laboratories, 9 cost analysis, 12-13 economic considerations, 9-10 financial perspective, 10 functions, 6-7,8t in quality assurance-quality control laboratories, 7,9 in research and development laboratories, 7 value assessment, 10-11 Laboratory information management systems, use in instrument automation, 4 Laboratory management, problems, 9 Linear polyethylene, relaxation behavior, 102 Linearized polystyrene reactor model matrix equations, 190 steady-state values, I89t Low-solids coatings, definition, 261

M Material balances, 233-234 Mathematical dynamic model development for emulsion polymerization processes applications, 224-226



320


Mathematical dynamic model development for emulsion polymerization processes—Continued extensions, 226 final mathematical model, 223 material balances, 222 molecular weight development, 222 particle distribution determination, 223,224t particle size development, 222 population balance approach, 222 Mathematical modeling for coatings acrylic polymerization model, 171-172,173 advantages, 175-176 definition, 171 factors influencing successful application, 177 solvent formulation system, 172,174-175 Mechanistic model for polymer property predicition, stages, 219 Menus for size-exclusion liquid chromatographic software auxiliary functions, 133 data handling, 133 housekeeping, 133 Microcomputers, acceptance, 170 Mixture design formulations, analysis and optimization, 58-72 Model development for free radical polymerization reactions decomposition reactions, 204,208 grams of indicator bonded, 209 moles of initiator, 209 number of initiator fragments attached to polymer molecules, 209 Model development and validation for optimization of curing for thermoset coatings kinetic model, 257-264 network structure model, 261-265 Molecular modeling at the bench, 36-37 current uses, 37 goals, 38 polymer model building, 34,35f,36f polymeric systems, 31-38 tools, 32-34 Molecular modeling tools, 32-34 Monodispersed approximation model, description, 220 Multiresponse mixture optimization choice of an algorithm, 66 complex algorithm-desirability function optimization, 69-70,71-72f noniterative ordering, 66,68 sequential generation, 66,68 N Nelder-Mead simplex algorithm, application and description, 244

Net present value calculation for hypothetical laboratory information management system, I4,15t definition, 13-14 Network structure model for cure optimization description, 261-262 extent of reaction, 261 Noniterative ordering technique advantages and disadvantages, 68 description, 66,68

0 Optical microscopy, computer methods, 155-166 Oven optimization for curing cure response determination, 268-269 cure uniformity vs. minimum heating rate constant, 269,270f,271 cure window vs. oven productivity, 271,273f minimum bake time vs. minimum heating rate constant, 271,272f

P Parameter determination for isochronal mechanical relaxation scans converged parameters, 98t,99f,100 implementation, 94-95,98-100 i n i t i a l parameter estimates, 95t,96-97f method, 92,94 Particle-size development rate expression for particle volume, 238 rate of change of polymer volume, 237-238 Patent activity data base, description, 19 Patent disclosure tracking data base activity f i l e , 19t patent description f i l e , 19t Payback, definition, 13 PBUILD, description, 34 Personal applications of data base management systems, examples, 22 Polymerization kinetics, initiation reactions and modeling, 202-217 Polymerization processes, problems, 219-220 P0LYRE0M, application, 84 Polystyrene reactor, control by state variable techniques, 187-201 Population balance approach, 220,222


321

INDEX


Population balances discussion, 234-235 nucleation term expression, 236 total property balance equation, 236 PRANDOM, description, 34 Program A, l i s t , 297 Program B description, 297 l i s t , 301 Program C l i s t , 308 model for self-condensation of 2,4-dimethylol-o-cresol, 306-308, 309f Project activity monitoring system, description, 18 PROPHET, description, 23-24

Q Quality assurance-quality control laboratories economics of laboratory information management systems, 9-10 se of laboratory information management systems, 7,9 alue of laboratory information management systems, 11 Quantile plots, applications, 137,139

R

Research and development laboratories economics of laboratory information management systems, 9 use of laboratory information management systems, 7 value of laboratory information management systems, 10-11 Rate constant determination for curing concentration determination, 244 contour plot for blocked isocyanate, 246,248f contour plot for constant values, 244,245f,246,247f contour plot using normalization, 250,252f,253,254f effectiveness, 244 experimental, 243 isocyanate absorbance vs. time, 250 isothermal cure curves, 246,247f kinetics analysis flow chart, 244 objective funcion for blocked isocyanate, 246,248f rate constants for blocked isocyanate, 246,249f

Rate constant determination for curing—Continued residual plot for blocked isocyanate, 246,249f,250 simplest case, 244 t r i a l curve from contour plot valley, 250,253,254f t r i a l curves, 250,251f Reaction control language of batch control system basic commands, 182,I83f,I85f macros, 184,185-186f overview, 182 parallel operation and flow control, 182,184 Relaxation processes dynamic shear response of isotactic polypropylenes, 100,101f relaxation behavior of linear polyethylene, 102 relaxation strength vs. crystallinity, 100,102,103f Research data management, packaged software, 23-30 Response contours, advantages, 60 Robotics systems, use in instrument automation, 3-4 RS/1 applications, 29-30 data analysis, 25,26f data management, 24 description, 23 ease of use, 25,27-28f extensibility, 29 flexibility, 29 graphics, 25,26f modeling, 25 statistics, 25 text, 25 S Savitsky-Golay method of smoothing, advantages, 8l,83f Scientific software applications, 29-30 data analysis, 25,26f early forms, 24 ease of use, 24 extensibility, 29 flexibility, 29 future developments, 30 graphics, 25,26f modeling, 24 statistics, 25 text, 24 Scientific software packages, advances, 23-30 Self-condensation of 2-dimethylol-o-cresol agreement between calculated and experimental results, 302



322


Self-condensation of 2-dimethylol-ocresol—Continued effect of ortho vs, para methylol groups, 289 model involving individual species, 306-310 number of species in system, 302,306 optimization using program B and STEPIT, 299,300f,301 path to optimization process, 302,303-305t reaction under mild conditions, 288-289 simple model using continuous system modeling program, 292-306 Sequential generation technique, advantages and disadvantages, 68 Silicone acrylate copolymers, applications, 39 Silicone acrylate oligomers behavior study by designed experimental techniques, 40-56 synthesis, 40,41f SIMPLEX program, use in oven optimization, 268-269 Single-response mixture optimization analysis of four-component pesticide mixture, 63-64,65f complex method, 62-63 optimization of 11-component glass formulation, 64,66,67f optimization of four-component flare mixture, 63 Size-exclusion liquid chromatography, software for data collection and analysis, 130-139 Software for size-exclusion liquid chromatography calibration, 137 data handling functions, 134-135,136f data reduction functions, 135,137,138f future directions, 137,139 hardware overview, 131-138 menus, 131,132f,133-134 shell structure, 133 Software for X-ray pole figure studies access to system, 143 data collection tasks, 146-150 data display functions, 150-151,152f data handling, 143,!44f,145-146 data processing, 151 extension to other computers, 151,153 future directions, 153 modules for pole figure facility, 142-143,I44f Solvent formulation system for coatings, 172,174-175

STEPIT, application, 299 Stereology basic theory of stereology, I60,l62t computer print out, I62,l63f,l66f data collection and analysis, 162 instrumentation, 160,161f parameter, 162t plots of parameters, I64,l65f STRESS program break point, 124-125 fracture analysis, 125 outlier identification, 125-126 stress, 124 work at break, 125 yield strength, 124 Suspension polymerization of styrene data analysis, 210-217 equations for intantaneous polymer properties, 204,206t literature data, 204,205t measured and molecular weight averages, 204,207f measured conversions and calculated polymerization rates, 204,207f model development, 204,208-210 Synthesis of silicone acrylate oligomers, experimental, 40,41f System configuration for tensile testing, 123-124

T

Task automation definition, 4 global planning system, 4-5 vs. instrument automation, 2 office automation tools, 4 two sides of the laboratory, 4 Tensile tester, automated analysis system, 123-128 Tensile testing data analysis program, 124-125 editing and reporting capability, 126,127f fracture analysis, 125 importance, 123 outlier identification, 125-126 plotting capability, 126,128f system configuration, 123-124 Thermoset coatings, optimization of bake conditions, 256-273

V Variance calculation, 78


INDEX

323


Variance—Continued calculation of 95% confidence limits, 78,79t summary of r values, 78,79t Viscoelastic device-computer interface advantages, 76-77 error estimation, 84,86 estimates of experimental error, 78,79t,80f,81 polymer studied, 77-78 smoothing functions, 8l,83f software package, 84 viscoelastic measurements, 77 viscoelastic properties of blends, 84,85f,87f Viscoelastic measurements log real modulus vs. temperature, 78,80f

Viscoelastic measurements—Continued signal-to-noise ratio, 81,82f smoothing, 8l,83f Viscoelastic properties effect of temperature, 86,87f vs. polymer structure, 86 vs. properties of pure components, 86 Viscoelastic properties of blends, function of temperature, 84,85f,87f

X X-ray orientation studies, software, 140-153

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Computer Applications in the Polymer Laboratory

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